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1 Health significance of drinking water calcium and magnesium František Kožíšek, M.D.

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1Health significance of drinking water calcium and magnesiumFrantišek Kožíšek,
M.D., Ph.D.National Institute of Public HealthFebruary 2003IntroductionDrinking
water quality is currently defined only as the absence or a strictly limited
presence of certain undesirable substances, however, distilled or demineralized
water can hardly be considered as an ideal of good drinking water. Drinking
water is a complex system of mineral substances and gases dissolved in water.
Calcium (Ca) and magnesium (Mg) are among the important and most thoroughly
studied natural water constituents.The present contribution summarizes the
existing knowledge of health significance of drinking water Ca and Mg and the
attempts to reflect it in regulation and suggests how to bridge the regulatory
gaps in this field.Calcium, magnesium and water hardnessIf we want to work on
calcium and magnesium in drinking water, a third parameter is to be taken into
account: water hardness, even if this term is incorrect and obsolete from a
strictly chemical point of view. That is to say that both of these elements
largely have not been analysed individually in drinking water in the past, but
just non-specifically in summary as hardness. This approach was applied in many
studies focused on health effects of this “water factor”.Since the definition of
water hardness is approached either analytically or technologically, it was not
and still has not been defined in a unified manner, and as with other
parameters, multiple definitions have been available and multiple units have
been used to express it (German, French, and English degrees; equivalent CaCO3or
CaO in mg/l). Initially, water hardness was understood to be a measure of the
capacity of water to precipitate soap, which is in practice the sum of
concentrations of all polyvalent cations present in water (Ca, Mg, Sr, Ba, Fe,
Al, Mn, etc.); nevertheless, since the other ions (apart from Ca and Mg) play a
minor role in this regard, later it has been generally accepted that hardness is
defined as the sum of the Ca and Mg concentrations, determined by the EDTA
titrimetric method, and expressed in mmol/l (ISO, 1984) or as CaCO3equivalent in
mg/l (Standard Methods, 1998), less frequently as the CaO equivalent.From the
technical point of view, multiple different scales of water hardness were
suggested (e.g. very soft – soft – medium hard – hard – very hard). Expectedly,
both extreme degrees (i.e. very soft and very hard) are considered as
undesirable concordantly from the technical and health points of view, but the
optimum Ca and Mg water levels are not easy to determine since the health
requirements may not coincide with the technical ones.Calcium and magnesium
presence in watersWater calcium and magnesium result from decomposition of
calcium and magnesium aluminosilicates and, at higher concentrations, from
dissolution of limestone, magnesium limestone, magnesite, gypsum and other
minerals. Anthropogenenic contamination of drinking water sources with calcium
and magnesium is not common but drinking water may
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2be intentionally supplemented with these elements while treated, as happens
with deacidification of underground waters by means of calcium hydroxide or
filtration through different compounds counteracting acidity such as CaCO3,
MgCO3and MgO, and possibly also with stabilization of low-mineralized waters by
addition of CaO and CO2.In low- and medium-mineralized underground and surface
waters (as drinking waters are), calcium and magnesium are mainly present as
simple ions Ca2+and Mg2+, the Ca levels varying from tens to hundreds of mg/l
and the Mg concentrations varying from units to tens of mg/l.Magnesium is
usually less abundant in waters than calcium, which is easy to understand since
magnesium is found in the Earth’s crust in much lower amounts as compared with
calcium. In common underground and surface waters the weight concentration of Ca
is usually several times higher compared to that of Mg, the Ca to Mg ratio
reaching up to 10. Nevertheless, a common Ca to Mg ratio is about 4, which
corresponds to a substance ratio of 2.4 (Pitter, 1999).Physiological role of
calcium and magnesium in the human body Both of these elements are essential for
the human body. Calcium is part of bones and teeth. In addition, it plays a role
in neuromuscular excitability (decreases it), good function of the conducting
myocardial system, heart and muscle contractility, intracellular information
transmission and blood coagulability. Osteoporosis and osteomalacia are the most
common manifestations of calcium deficiency; a less common but proved disorder
attributable to Ca deficiency is hypertension. Based on newly acquired
epidemiological data, implication of Ca deficiency in other disorders is
currently being discussed. The recommended Ca daily intakefor adults ranges
between 700 and 1000 mg (Scientific Committee for Food, 1993; Committee on
Dietary Reference Intake, 1997). Some population groups may need a higher
intake.Magnesium plays an important role as a cofactor and activator of more
than 300 enzymatic reactions including glycolysis, ATP metabolism, transport of
elements such as Na, K and Ca through membranes, synthesis of proteins and
nucleic acids, neuromuscular excitability and muscle contraction etc. It acts as
a natural antagonist of calcium. Magnesium deficiency increases risk to humans
of developing various pathological conditions such as vasoconstrictions,
hypertension, cardiac arrhythmia, atherosclerotic vascular disease, acute
myocardial infarction, eclampsia in pregnant women, possibly diabetes mellitus
of type II and osteoporosis (Rude, 1998; Innerarity, 2000; Saris et al, 2000).
These relationships reported in multiple clinical and epidemiological studies
have recently been more and more supported by the results of many experimental
studies on animals (Sherer et al, 2001). The recommended magnesium daily intake
for an adult is about 300-400 mg (Scientific Committee for Food, 1993; Committee
on Dietary Reference Intake, 1997). Beginnings of research into health
significance of water hardnessThat drinking water is also an important source of
essential (i.e. essential to life) elements such as Ca and Mg was already known
before world war II (Kabrhel, 1927; Widdowson, 1944). The significance of
drinking water calcium for nutrition was underlined in the 1940’s by a German
nutritionist R.Hauschka who recommended sodium hydrogen sulphate to be added to
water prior to boiling in order to maintain the level of dissolved calcium and
to prevent loss of calcium due to precipitation (Hauschka, 1951).
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3Health significance of water hardness was directly evidenced in the late
1950’s. The relationship between water hardness and the incidence of vascular
diseases was first described by a Japanese chemist Kobayashi (Kobayashi, 1957)
who showed, based on epidemiological analysis, higher mortality rates from
cerebrovascular diseases (stroke) in the areas of Japanese rivers with more acid
(i.e. softer) water compared to those with more alkaline (i.e. harder) water
used for drinking purposes.Several studies followed and most of them confirmed
an inverse correlation between water hardness and mortality from cardiovascular
diseases (CVD). Among the best known studies were those by H.A.Schroeder who
demonstrated, among others, correlation between mortality from CVD in males aged
45-64 years and water hardness in 163 largest cities of the USA (Schroeder,
1960) and summarized his results using the following compelling dictum: „soft
water, hard arteries“. Other studies were published by Morris in Wales (Morris
et al, 1961) and Canadian, Finnish, Italian, Swedish and other authors. A review
of most relevant papers of the 1960’s is given e.g. in a WHO Bulletin (Masironi
et al, 1972) or by Sharrett and Feinleib (Sharrett et al, 1975).An interesting
British study (Crawford et al, 1971) focused on variation in mortality from CVD
depending on water hardness in 11 British cities between 1950 and 1960. Water
hardness increased in five cities and decreased in six cities. Within the given
period mortality from CVD in the UK increased by 10% on average compared to 20%
in the cities supplied with softer water than before and compared to 8,5% only
in the cities supplied with harder water than before.It is interesting to note
that significant differences in cardiovascular pathology and the magnesium
content of the cardiac muscle were found between males who had died from
infarction and those who had been victims of traffic accidents and between those
living in the areas with soft or hard water: harder water was associated with a
higher magnesium content of the cardiac muscle (Crawford et al, 1967; Anderson
et al, 1973; Neri et al, 1975; and six other studies given in Rubenowitz et al,
1999). Correlation between the water Mg level of and the Mg content of skeletal
muscles is also described in a Swedish study of the late 1980‘s (Landin et al,
1989).Within the first two decades of research into water hardness in
association with CVD more than 100 papers were published (Hewitt et al,
1980).From the very beginning the crucial question was what the „unknown water
factor“ responsible for the positive/negative effect on CVD morbidity was. Apart
from the calcium and magnesium content alone as the major factor implicated in
water hardness and possibly the Ca to Mg ratio, a role played by other trace
elements both beneficial to health (Li, Zn, Co, Cu, Sn, Mn, Cr ...) and toxic
(Pb, Cd, Hg) was considered; nevertheless, no significant correlation between
the content of any of these elements in water and CVD morbidity was found or
repeatedly confirmed in other studies. Attention was paid not only to the theory
of the content of these elements at source but also to higher corrosive
potential of soft water that can support higher leakage of toxic compounds from
the water pipe network.Over the years, evidence has accumulated that magnesium
is the major beneficial agent involved, while calcium has only a supportive
effect against CVD (Eisenberg, 1992). Although only two out of three studies
have shown correlation between cardiovascular
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4mortality and water hardness, the studies carried out on the water magnesium
alone have practically all shown an inverse correlation between cardiovascular
mortality and water magnesium level (Durlach et al, 1985).In the late 1970’s,
the issue of an optimum composition of drinking water, particularly if obtained
by desalination, was in the centre of attention of the WHO. The WHO also
emphasized the importance of mineral composition of drinking water and warned
e.g. against the use of cation exchange sodium cycle softening in water
treatment (WHO, 1978; WHO, 1979). An international group of experts who met in
1975 under the auspicies of the European Commission also concluded: „although it
has not yet been possible to establish any relationship between the cause and
effect, the existence on an association between water hardness and mortality
cannot be dismissed“ (Amavis et al, 1976).The 1980’s and criticisms of the
existing epidemiological studiesIn the 1980’s the wave of interest in the effect
of water hardness on CVD morbidity rather subsided; it seemed that any new
insight into the issue could not be expected. The focus was on confirming the
role of magnesium as a crucial factor of hardness and on first attempts of more
general quantification of its protective effect (see below).What made a new
challenge to publication of further studies in the 1990’s were criticisms of the
existing studies (e.g. Comstock, 1980). Such criticisms were partly justified
since based on new epidemiological methods: they revealed methodical drawbacks
of the previous studies that were mostly ecologic. This means that they
evaluated morbidity at a population group-based level rather than at an
individual-based level and did not establish individual exposure to calcium and
magnesium from water. Some of the studies did not even analyse water for the
calcium and magnesium content, but focused on water hardness only, and
consequently, did not allow to specify the implication of either calcium or
magnesium. In other studies, the confounders possibly involved in CVD morbidity
such as age, socio-economic factors, alcohol consumption, eating habits,
climatic conditions etc. were not adequately taken into account. Nevertheless,
most studies dealing with individual exposure confirmed an inverse correlation
between the drinking water Mg level and the risk to population of developing CVD
as described in ecologic studies, e.g. a vast Finnish cohort study (Punsar et
al, 1979), a case-control study carried out in the same country (Luoma et al,
1983), an American study (Zeighami et al, 1985) and a USSR study (Novikov et al,
1983).The criticisms also pointed out that not all studies then had found
correlation between water hardness and CVD morbidity. This is less compelling
since water hardness is only one - and probably not the crucial one – of
multiple factors possibly involved in CVD morbidity. If other factors which are
not taken into account prevail, the effect of water hardness may be biased. In
some cases, such „failures“ to document water hardness effect were
retrospectively explained by a low level of crucial magnesium in hard water and
subsequent insignificant difference in the Mg content between soft and hard
water (Bar-Dayan et al, 1997). Such explanation seems to be also applicable to
the results of a Norvegian ecologic study (Flaten et al, 1991) showing even a
slightly positive correlation between the magnesium content of drinking water
and CVD morbidity, but all the areas studied had extremely soft water containing
less than 2 mg Mg/l.
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5These criticisms seem to be at the origin of the WHO position adopted with
respect to the last Guidelines for drinking water quality elaborated in
1990-1993. In spite of former enthusiastic opinion of the WHO on water hardness
importance, the Guidelines cautiously admitted some weak relationships between
hardness and health, but concluded: “the available data are inadequate to permit
the conclusion that association is causal. No health-based guideline value for
water hardness is proposed”. Only sensorial and technical disadvantages of
extremely hard and extremely soft water were specified (WHO, 1993). Nonetheless,
some studies on water hardness published in the 1980’s are referred to in the
2ndvolume of the Guidelines (WHO, 1996); surprisingly, some less important or
methodically less developed studies (e.g. Kubis, 1985) are listed among the
references rather than other studies of highest epidemiological significance.The

1990‘s: correlation with cardiovascular diseases confirmed and new knowledgeMost


new epidemiological studies of the 1990’s were able to specify the effect of
either calcium or magnesium and also focused on morbidity other than CVD;
studies meeting the current methodical standards were published in high impact
epidemiological journals. Protective effect of both drinking water magnesium and
calcium against CVD was confirmed and more data on beneficial effect of these
elements in drinking water on human health are presented. A review of all
epidemiological studies of 1990-2000 and some older ones dealing with the
relationship between drinking water composition and CVD is given by Sauvant and
Pepin (Sauvant et al, 2002).A Swedish ecologic study found a significant inverse
correlation between water hardness and mortality from CVD for both males and
females and a significant correlation between the drinking water magnesium level
and mortality from CVD in males (Rylander et al, 1991). In all districts where
the drinking water magnesium level was higher than 8 mg/l (but not higher than
15 mg/l), the CVD mortality rates were lower. Another Swedish case-control study
focused on the effect of the drinking water Mg and Ca levels on mortality from
acute myocardial infarction (AMI) in females showed a statistically
significantly lower mortality rate (by 34%) in the areas supplied with water
containing more calcium (> 70 mg/l) as compared to those where the drinking
water calcium level was < 31 mg/l; a similar finding was presented independently
for magnesium: the mortality rate was by 30% lower in the areas where the water
Mg content was > 9,9 mg/l compared to those where the water Mg content was < 3,4
mg/l (Rubenowitz et al, 1999). Another Swedish case-control study showed a
significant correlation between male mortality from AMI the Mg content of water.
Cases were 854 men from 17 municipalities in the southern part of Sweden who had
died of AMI between ages 50 and 69 years during the period 1982-1989. The
controls were 989 men of the same age in the same area who died from cancer
during the same period. Only men who consumed water supplied from municipal
waterworks were included in the study. The group with hard water (> 9,8 mg Mg/l)

had a mortality rate from AMI by 35% lower as compared with the consumers of
soft water (< 3,5 mg Mg/l). Any correlation with the water Ca content was not
reported (Rubenowitz et al, 1996).Another study of the same type and by the same
authors focused on correlation between the drinking water Mg and Ca levels and
morbidity and mortality from AMI in 823 males and females aged 50-74 years in 18
Swedish districts, who had developed AMI between October 1, 1994 and June 30,
1996 (Rubenowitz et al, 2000). The study took into account both
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6individual exposure to Ca and Mg from water and food and other known risk
factors for AMI likely to bias the correlation, if any. Although for calcium the
correlation with AMI was not confirmed, magnesium proved to reduce the risk
level by 7.6 % in the group of the quartile with the highest water Mg level (≥
8,3 mg/l) compared to groups exposed to water containing lower levels of
magnesium. Although the total AMI rates were similar in all four groups, the
persons enrolled in the group with the highest water Mg level had a risk level
of death from AMI by a third lower (odds ratio 0.64) as compared to the groups
consuming water containing less Mg than 8.3 mg/l. Multivariate analyses showed
that the correlation found is not caused by other known risk factors. This
finding supports the hypothesis that magnesium prevents primarily sudden death
from AMI, rather than all ischemic heart disease deaths or the risk of suffering
an AMI.Another ecologic Swedish study analyzing causes of a marked difference in
anti CVD drugs consumption between two districts found the difference in water
hardness to be one of possible causes in this regard (Oreberg et al, 1992).
Another ecologic study from seven Central Swedish districts ascribes higher
mortality rates from IHD (by 41%) and from stroke (by 14 %) to water softness
(Nerbrand et al, 1992).In contrast to this series of Swedish studies confirming
the correlation mentioned above, another Swedish study surprisingly concluded
that in cold areas in Sweden, the climate (more precisely the so-called cold
index) has a higher effect on mortality from CVD than water hardness (Gyllerup
et al, 1991). An ecologic study of Tennessee (Erb, 1997) found mortality from
CVD to be by 19% lower in the areas supplied with hard water (161 mg CaCO3/l)
compared to soft water (39 mg CaCO3/l). Even more compelling were the
conclusions of an extensive study (a total of 3013 cases of 1973-1983) carried
out in the former German Democratic Republic: in an area supplied with very hard
water (Mg content close to 30 mg/l) the incidence rate of AMI was 20.6 per 10000
population while in the areas supplied with soft water (Mg content about 3 mg/l)
the rate was as high as 32.7; the difference was even higher in younger age
categories (Teitge, 1990). A Serbian environmental study (Maksimovic et al,
1998) also found out a marked difference in mortality from CVD between the
population groups supplied with drinking water with a „low“ Mg level (less than
20 mg/l) and a high Mg level (52 to 68 mg/l).The difference in the drinking
water Mg level as the most probable explanation for different rates of
myocardial calcifications in persons who died from AMI is reported by authors of
a study carried out in Salt Lake City and Washington D.C. (Bloom et al, 1989).
The significance of a low drinking water magnesium level as a risk factor for
CVD particularly in males is underlined by Rylander’s review article (Rylander,
1996). Multiple past and recent epidemiological studies reported lower rates of
sudden deaths from CVD (including sudden deaths in infants) in the areas with
harder water (Crawford et al, 1972; Anderson et al, 1975; Eisenberg, 1992;
Bernardi et al, 1995; Garzon et al, 1998). It is hypothesized that magnesium
deficiency is implicated in cardiovascular spasms and cardiac arrhythmias
leading to death. Only a statistically slightly significant link between water
hardness and geographical differences in mortality from cerebrovascular diseases
was revealed in a study of North Dakota (Dzik, 1989); similar findings were
reported by a French environmental study not
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7only for cerebrovascular diseases but also for IHD (Sauvant et al, 2000);
nevertheless, water hardness was taken as a general factor regardless of Ca to
Mg levels. While health effects of most chemicals commonly found in drinking
water manifest themselves after a long exposure only, the effects of calcium and
in particular those of magnesium on the cardiovascular system are believed to
reflect the current exposure which means that a couple of monts are sufficient
for „adaptation“ to a new source of water with low content of magnesium and/or
calcium. Adaptation here does not mean adaptation of the organism to the water
of an inadequate composition but time within which the intake of drinking water
of inadequate composition may manifest itself by a disorder of consumer’s health
(Rubenowitz et al, 2000). Illustrative are cases among Czech and Slovak
population who started to use reverse osmosis-based systems for final treatment
of drinking water at their home outlets in 2000-2002 and several weeks later
reported different health complaints suggestive of acute magnesium
deficiency.New knowledge of protective effects of drinking water calcium and
magnesiumCalcium alone probably has a positive protective effect against some
neurological disturbances in the elderly as evidenced by a French case study.
The results in a region supplied with drinking water containing Ca > 75 mg/l
were by 20% more favourable compared to a drinking water Ca level < 75 mg/l
(Jacqmin et al, 1994). A Mallorca study reported that children in the areas
supplied with drinking water containing higher calcium levels showed
statistically significantly lower incidence of fractures compared to those
supplied with water poorer in calcium, if drinking water fluorides and
socio-economic conditions were taken into account (Verd Vallespir et al,
1992).While in males no study evidenced that the water calcium level could have
an effect on the risk for death from myocardial infarction, in females a low
water calcium level proved to be one of the risk factors in this regard
(Rubenowitz et al, 1999). Reality of such relationship is supported by the known
fact that calcium deficiency may cause hypertension. Meta-analysis of several
studies including almost 40 thousand population showed an inverse correlation
between the calcium intake from food and blood pressure (Capuccio et al, 1995).
Moreover, several mechanisms are known by which the calcium implication in blood
pressure fall can be explained (Rubenowitz et al, 1999).An inverse correlation
between the calcium intake with food and blood pressure was also described in
pregnant women in whom calcium supplementation is effective in blood pressure
reduction. Higher intake of calcium is believed to decrease smooth muscle
contractility and tonus, which clinically results in lower blood pressure and
lower rate of pre-term births. In this light, an epidemiological combined
ecologic case-control study was carried out in Taiwan in 1781 females:
relationship between the drinking water calcium level and birth weight of first
borns was analyzed. Drinking water calcium was found to be a beneficial
protective factor statistically significantly reducing the risk for pre-term
birth and low birth weight (Yang et al, 2002).An inverse correlation between the
intake of an element with food and blood pressure wasconfirmed in most studies
also for magnesium (Mizushima et al, 1998).A low magnesium content of drinking
water was found to be a risk factor for motor neuron disease (Iwami et al, 1994)

and preeclampsia in pregnant women (Melles et al, 1992).


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8Discordant results were obtained in the studies dealing with correlation
between the drinking water magnesium level and the incidence of diabetes
mellitus. Although a Taiwan study (Yang et al, 1999a) reported protective effect
of magnesium or lower incidence of diabetes mellitus in the areas supplied with
water with higher magnesium levels, an American study (Joslyn et al, 1990) did
not find such a correlation.A low intake of Ca and Mg with drinking water seems
to be a risk factor for amyotrophic lateral sclerosis (Yasui et al, 1997), while
higher levels of these elements in drinking water may have protective effect
against caries and periodontal disease even if the fluorides content of water is
low (Skljar et al, 1987). Russian epidemiological studies (predominantly of
ecologic type) found significantly higher incidence rates of hypertension, IHD,
adrenergic function disturbances, gastric and duodenal ulcer and other diseases
in the areas with soft water (less than 1.5 mmol/l) (Loseva et al, 1988; Plitman
et al, 1989; Lutai, 1992).German study did not find any correlation between the
incidence of endemic goitre and the drinking water calcium and magnesium levels
(Sauerbrey et al, 1989), while a Russian ecologic study reported higher
incidence of goitre in the population supplied with low-mineralized water
(Lutai, 1992).Water hardness and cancer. In the late 1990’s several
epidemiological studies were carried out in Taiwan to focus on relationships
between drinking water hardness and mortality from various diseases showing
significant geografical variation. Magnesium was found to have protective effect
against cerebrovascular diseases (Yang, 1998) and hypertension (Yang et al,
1999b), water hardness showed protective effect against CVD (Yang et al, 1996),
cancer of oesophagus (Yang et al, 1999c), cancer of pancreas (Yang et al,
1999d), cancer of rectum (Yang et al, 1999e) and breast cancer (Yang et al,
2000), drinking water calcium proved protective against colorectal cancer (Yang
et al, 1997) and gastric cancer (Yang et al, 1998). These were combined ecologic
case-control studies. Further studies from other countries are needed to confirm
these results. Although previous studies dealing with relationships between
water hardness and the incidence of cancer elsewhere in the world were mostly
suggestive of protective effect of hard water, the results were ambiguous as
stated in a review paper (Cantor, 1997) underlining the need for further studies
in this promising field. The epidemiological findings are supported by the
clinical discussion on positive role of calcium in both food and water in
colorectal cancer prevention (Pence, 1993).Antitoxic effect of calcium and
magnesiumCalcium and to a lower extent also magnesium in both drinking water and
food were previously found to have a beneficial antitoxic effect since they
prevent – via either a direct reaction resulting in an nonabsorbable compound or
competition for binding sites –absorption or reduce harmful effects of some
toxic elements such as lead, cadmium etc. (Thompson, 1970; Levander, 1977;
Oehme, 1979; Hopps et al, 1986; Nadeenko et al, 1987; Plitman et al, 1989;
Durlach et al, 1989). Nevertheless, this protective effect is limited
quantitatively.Disproportion between the high protective effect and low
nutritive contribution of drinking water Mg and CaA detailed critical analysis
of the studies on the drinking water magnesium level and the incidence of IHD
was presented by Marx and Neutra (Marx et al, 1997). As in other studies
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9(Neutra, 1999), the authors focus on how the relatively low magnesium intake
with drinking water (usually less than 10 % of the total daily magnesium intake)
can reduce mortality from CVD by even 30 %. Several explanations are possible
and several causes may be implicated at a time. It is generally known that
modern refined food does not contain enough magnesium and that most adult
population either fail to cover or just cover the recommended daily intake of
magnesium and therefore live close to the permanent Mg deficiency. These
conclusions were concordantly drawn from surveys carried out in many
industrialized countries. For instance, the Ministry of Agriculture of the USA,
based on surveys among 37 thousand population in the late 1970’s, reported the
recommended daily intake of magnesium to be met or exceeded in 25 % of them
only; in contrast, as many as 39 % of population had lower magnesium intake than
70 % of the recommended daily intake (Marier, 1986). Subsequent studies
confirmed these findings and reported that most Americans intake less Ca and Mg
than recommended and that even many subjects took less than 80% of the
recommended dietary allowances (RDA) for Mg – it is to be noted that in general,
„as of this date, RDAs have not addressed prevention of chronic diseases“ (Marx
et al, 1997). In the Czech Republic, the calcium and magnesium intake with food
is close to the lower limit of the recommended daily intake and the deficiency
may easily manifest itself in some population groups. In the year 2000, the the
recommended daily intakes for Mg and Ca were covered to 83 % and 91 %,
respectively (Ruprich et al, 2001). In Germany, insufficient intake of magnesium
was recorded in 15 % of children on average: it reached 25 % in children in
northern Germany supplied usually with soft water, i.e. was 3 to 4 times higher
as compared with the percentage in southern regions supplied mostly with water
rich in magnesium and calcium (Schimatschek, 2003).Under such conditions, even
the relatively low intake of Mg with drinking water may be of relevance for
prevention or reduction of Mg deficiency. Let’s have a closer insight into that
„low intake“. In Ontario, it was found that the difference in Mg intake from the
hardest and the softest drinking waters was 53 mg Mg/day (Marier et al, 1985),
which is definitely more than 10% of the total intake. Absorption of magnesium
from food in the intestine is about 30%, while magnesium from water where it is
present in free cation form is absorbable to a higher extent - from 40 % to 60 %
as reported (Durlach et al, 1985; Durlach, 1988; Neutra, 1999; Sabatier et al,
2002), i.e. Mg absorbability from water is by 30 % higher compared to dietary
magnesium (Marx et al, 1997). Drinking water is also a relatively more suitable
source of Mg and Ca than food since it is generally true that the higher the
amount of these elements is available, the lower proportion of them is absorbed
(Böhmer et al, 2000; Sabatier et al, 2002).Soft water was proved to reduce
markedly the content of different elements (including Mg and Ca) in food if used
for cooking vegetables, meat and cereals (WHO, 1978; Haring et al, 1981; Oh et
al, 1986; Durlach, 1988). Up to 60% for magnesium and calcium! In contrast, if
used for cooking, hard water is responsible for much lower loss of elements or
may even fortify the calcium content of the food prepared. Therefore, in the
areas supplied with soft water, we have to take into account not only a lower
intake of magnesium and calcium from drinking water but also a lower intake of
magnesium and calcium from food due to cooking in such water. All these aspects
contribute to better understanding of the „relatively low intake“ of magnesium
from drinking water. Anyway, protective effect of drinking water magnesium may
not be linearly (quantitatively) proportional to the share of drinking water in
the total intake of this element.
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10Durlach (Durlach, 1988; Durlach et al, 1989) repeatedly underlines the
so-called qualitative importance of water magnesium. Its higher bioavailability
as compared with food magnesium is not due only to its increased GIT absorption
(better biodisposability), but also to its increased utilization probably
resulting from the biologically advantageous (hexahydrated) form of water
magnesium (Theophanides et al, 1990).Repeated tests on animals yielded highly
surprising results: the animals given the element studied (i.e. Zn or Mg) with
drinking water showed statistically significantly higher increase of this
element in the serum than those given a much higher amount of these elements
with food and demineralized water to drink. Based on experiments and clinical
observation that mineral deficiency in patients receiving balanced intravenous
nutrition (to be diluted with distilled water) where intestinal absorption does
not need to be considered, the authors presume that demineralized water intake
is responsible for increased elimination of minerals from the organism (Robbins
et al, 1981). A similar mechanism could also apply to soft low-mineralized
water.Some researchers say that the differences in mortality from CVD (or those
in the incidence of other diseases) could be explained by the effect of other
confounders such as physical activity, eating habits, obesity, alcohol
consumption, socio-economic conditions etc. and that these confounders may give
a false positive idea of the effect of calcium or magnesium in water. The most
compelling counter-argument to these objections is that there is no reason to
expect that there could be any correlation between the lifestyle factors
mentioned above and water hardness resulting from the environmental
conditions.Magnesium: dose (concentration in water) – response relationshipFirst
attempts to quantify the protective effect of water magnesium date back to the
1960’s. For instance, based on Schroeder’s American studies, it was estimated
that an increase in the water magnesium level by about 8 mg/l led to reduction
of mortality from all CVD by about 10%; similarly, based on a South African
study, it was estimated that an increase in drinking water magnesium by 6 mg/l
led to reduction of mortality from IHD equally by about 10%(Marier et al, 1985).
An extensive East German study reported an even lower value: if drinking water
magnesium is reduced by about 4.5 mg/l, the incidence of myocardial infarction
increases by 10% (Teitge, 1990).Pocock et al. (1980) described a negative
non-linear relationship between CVD mortality and water hardness, based on the
data from a British Regional Heart Study (regional variations in cardiovascular
mortality in 253 towns during 1969-73). The adjusted standardised mortality
ratios decreased steadily in moving from a hardness of 0.1 to 1.7 mmol/l (10 to
170 mg CaCO3/l) but changed little in moving from 1.7 to 2.9 mmol/l (170 to 290
mg/l) or more. The model estimated that in the range below 1.7 mmol/l an
increase in total hardness of 1 mmol/l – say from 0.5 to 1.5 mmol/l – while
keeping other variables constant should result in a 7.2 % decrease in CVD
mortality, whereas there was no evidence of an equivalent decrease beyond 1.7
mmol/l.Out of six studies analyzed by Marx and Neutra (Marx et al, 1997) the
decrease in the absolute cardiovascular mortality ranged from 0.1 per mg (of Mg)
per 100,000 population in a Los Angeles study (Allwright et al, 1974) to
20.0/mg/100,000 in a Finnish study (Punsar et al, 1979). The relative risk
decrease ranged from 0.001 to 0.034 per mg of magnesium.Several authors
attempted to represent this relationship diagrammatically.
Page 11
11Figure 1 taken from Rylander (Rylander, 1996) shows correlation between CVD
mortality in males and drinking water magnesium levels, based on German (Teitge,
1990), Swedish (Rylander et al, 1991) and South African (Leary et al, 1983)
studies.Figure 2 taken from the study by Marx and Neutra (Marx et al, 1997)
shows relative risk of ischemic heart disease as a function of water magnesium
concentration in five rate-based studies (Allwright et al, 1974; Leary et al,
1983; Punsar et al, 1979; Teitge, 1990; Rylander et al, 1991).Swedish
researchers presume that the protective effect of drinking water magnesium
against CVD mortality is of a threshold nature, more precisely that it starts
working from the values above about 8 mg/l (Rubenowitz et al, 2000). This
conclusion is drawn from Swedish studies (Rylander et al, 1991; Rubenowitz et
al, 1996, 1999 a 2000), one South African study (Leary et al, 1983) and one
German study (Teitge, 1990). Nevertheless, this does not mean that different
magnesium levels either above or below this limit would be associated with the
same risk. The opinion may be a point of departure for possible recommendations
for drinking water magnesium levels or legislative measures.
Page 12
12Significance of the magnesium to calcium ratioSince the 1960’s, some authors
consider the absolute content of both elements in water (diet) to be of the same
importance as the magnesium to calcium ratio (Seelig, 1964; Karppanen, 1981;
Durlach et al, 1989). Durlach’s recommendation that the Mg to Ca total intake
ratio should be 1 to 2 (Durlach, 1989) as required for the best Mg absorption
has still been valid. Theoretical derivation of the recommended Mg to Ca ratio
in water can be supported by several epidemiological studies suggestive of
negative effects of variations in this ratio in both directions: decrease in the
Mg to Ca ratio was associated with increasing risk for mortality from IHD and
AMI (Itokawa, 1991; Rubenowitz et al, 1996) while the increase in the Mg to Ca
ratio was associated with increasing risk for gastric cancer (Sakamoto et al,
1997). Nevertheless, any definitive conclusions or recommendations cannot be
drawn from the data available; a low water Mg to Ca ratio was always associated
with a low water Mg level and the water Mg level has proved to play a more
important role in risk reduction (e.g. for AMI) as compared with the Mg to Ca
ratio (Rubenowitz et al, 1996).Bioavailability of drinking water calcium and
magnesium Some non-professionals are of opinion, supported and spread mainly by
the manufacturers of devices for production of distilled and demineralized water
(Bragg et al, 1998), that the human body is not able to use the essential
minerals from drinking water, which in contrast clog up the body (similarly as
happens to the pipes) and cause harm to it. Nevertheless, no study is available
to support such idea. On the other hand, multiple studies have shown that
intestinal absorption of calcium from drinking or mineral water is as effective
or even more effective as compared with that from dairy products (e.g. Halpern
et al, 1991; Heaney et al,1994; Couzy et al, 1995; Van Dokkum et al, 1996;
Wynckel et al, 1997; Guillemant et al, 1997). Meta-analysis of the studies
published in 1966 – 1998 even evidenced that calcium absorption from mineral
water is statistically significantly higher than that from dairy products
(Böhmer et al, 2000). Based on this evidence, it was recommended to use waters
richer in calcium as an important additional source of calcium in menopausal
women, lactose intolerant people or those avoiding dairy products because of
their taste or high fat content.Not only absorbability is in question. Many
studies have documented that water calcium can be easily used by the body:
intake of drinking water rich in calcium correlated with higher bone density in
elderly women in France (Aptel et al, 1999); similar results were obtained in an
experiment with mineral water in menopausal women in Italy (Gennari, 1996;
Cepollaro et al, 1999); lower bone resorption and osteoporosis were observed in
women after drinking calcium rich water (Costi et al, 1999; Guillemant, 2000).
The already mentioned Spanish study (Verd Vallespir et al, 1992) found a lower
incidence of fractures in small school children of the areas supplied with
harder water.Bioavailability of water magnesium was documented by the studies of
the 1960’s and 1970’s that found a positive correlation between the drinking
water magnesium level and the magnesium content of the heart muscle (Crawford et
al, 1967; Neri et al, 1975); among more recent papers we can quote e.g. a
Swedish study (Rubenowitz et al, 1998). Three-week drinking of magnesium rich
water (120 mg/l) resulted in 79 patients in lower pain intensity and frequency
of migraine (Thomas et al, 1992). Similar results were obtained in a more recent
study by the same authors (Thomas et al, 2000) with 29 migraine patients and 18
controls. Two-week drinking of water containing 110 mg Mg /l confirmed good
usability of
Page 13
13water magnesium leading to higher levels of intracellular magnesium and
conservation of the serum magnesium level. Some balneological studies reported
positive effects of magnesium rich water, but it is to be noted that these were
based on short-term experiments (not longer than several weeks) focused on
therapeutic effects, in many cases with waters rich in total dissolved solids
and therefore, the results should be interpreted with caution with relation to
drinking water.Water hardness and urolithiasisThe key role of water in urinary
stone formation is generally accepted by the public; nevertheless, only the
quantitative facet of this idea is justified – insufficient intake of water and
other liquids, i.e. permanent dehydration, even if slight, surely increases the
risk for urolithiasis of all types. On the other hand, qualitative assessment
shows that the content of water minerals, more precisely of magnesium and
calcium, plays a less important role. Urinary stone formation is a process
involving multiple factors, i.e. not only intake of liquids, but also genetic
predisposition, eating habits, climatic and social conditions, gender,
etc.Several studies documented that higher water hardness is associated with
higher incidence of urolithiasis among the population supplied with such water;
in contrast, more studies found softer water to be associated with higher risk
for urolithiasis. Nevertheless, most recent epidemiological studies explain
those controversial results by differences in the study designs and say that
water hardness ranging between the values commonly reported for drinking water
is not a significant factor in urolithiasis (Singh et al, 1993; Ripa et al,
1995; Kohri et al, 1993; Kohri et al, 1989). Any correlation between water
hardness, or the drinking water calcium or magnesium level, and the incidence of
urolithiasis was not found in the last vast USA epidemiological study with 3270
patients (Schwartz et al, 2002).The quoted Japanese studies did not found that
the water calcium or magnesium levels alone had an effect on the incidence of
urolithiasis but did found that the Mg to Ca ratio had: one study reported the
lower Mg to Ca ratio to be associated with a higher risk for urolithiasis
regardless of type and the incidence of urolithiase to correlate with the type
of geological subsoil (Kohri et al, 1989) and another study found correlation
between the higher Mg to Ca ratio and higher incidence of infectious phosphate
urolithiasis (Kohri et al, 1993).Many experimental studies document that higher
water hardness does not pose any risk for urolithiasis (which is not true of
extreme water hardness beyond the range to be considered for drinking water –
see below) and confirm concordantly that intake of calcium rich water (or
magnesium rich water) reduces risk for calcium oxalate urolithiasis (Rodgers,
1997; Rodgers, 1998; Caudarella et al, 1998; Marangella et al, 1996;
Gutenbrunner et al, 1989; Ackermann et al, 1988; Sommariva et al, 1987). Intake
of such water is associated with higher urinary calcium elimination and at the
same time with lower urinary oxalate elimination probably due to oxalate bond to
calcium in the intestine with subsequent prevention of oxalate absorption and
enhanced oxalate elimination through feces.Nevertheless, these conclusions do
not apply to patients after urinary stone removal. Isolated experiments
suggested that intake of softer drinking water resulted in a lower rate of
recurrent urolithiasis (Bellizzi et al, 1999; Coen et al, 2001; Di Silverio et
al, 2000) but admitted at the same time that the results could not be
generalized and depended on multiple factors, e.g. whether water was given
between meals as in one of the studies above or during meals when, in contast,
harder water intake may have been associated with a lower rate of recurrences
Page 14
14(Bellizzi et al, 1999). Genetic predispositions and eating habits may play a
relevant role in this regard.High hardness (>5 mmol/l) which is not typical of
drinking water may be associated with higher risk for urinary and salivary stone
formation as documented by a Russian epidemiological study (Mudryi, 1999). The
author says that a long-term intake of drinking water harder than 5 mmol/l
results in a higher local blood supply in the kidneys and subsequent adaptation
of the filtration and resorption processes in the kidney. This is believed to be
protective reaction of the human body which may lead, if the conditions persist,
to alteration of the body‘s regulatory system with possible subsequent
development of urolithiasis and hypertension. Risk for urolithiasis was also
associated with intake of water of a hardness of 10.5 mmol/l (Ca 370 mg/l) as
documented by the already quoted Italian study (Coen et al, 2001).Cases of
urolithiasis and other complications, otherwise rarely reported at low age, were
described in infants whose feeding was prepared exclusively with calcium rich
mineral water (Ca 555 mg/l, Mg 110 mg/l, water hardness 18.4 mmol/l) and whose
calcium daily intake was consequently several times higher than recommended
(Saulnier et al, 2000).Harmful effects of hard waterNo evidence is available to
document harm to human health from harder drinking water. Perhaps only a high
magnesium content (hundreds of mg/l) coupled with a high sulphate content may
cause diarrhoea. Nevertheless, such cases are rather rare; other harmful health
effects due to high water hardness (e.g. the effects on the eliminatory system
as mentioned above) were observed in waters rich in dissolved solids (above 1000
mg/l) showing mineral levels which are not typical of most drinking waters.In
the areas of the Tula region supplied with drinking water harder than 5 mmol/l,
higher incidence rates of cholelithiasis, urolithiasis, arthrosis and
arthropathies as compared withthose supplied with softer water were reported
(Muzalevskaya et al, 1993). Another epidemiological study carried out in the
Tambov region found hard water (more than 4-5 mmol/l) to be possible cause of
higher incidence rates of some diseases including cancer (Golubev et al, 1994).
The results of the studies concerning the relationship between water hardness
and tumours are discordant, but most of them are supportive of protective effect
of harder water (see above). The quoted Russian studies did not assess possible
effect of higher levels of other dissolved minerals in drinking water
(increasing water hardness is usually coupled with the increasing total content
of dissolved solids).Hard water is also reported to cause increase in the risk
for atopic eczema in school children (McNally et al, 1998) which can probably be
explained by its higher drying effect on the skin (similar to that of
overchlorinated water), but in this case water is used externally and is not
intended for consumption.Sensorial disadvantages of hard and soft waterHigher
water hardness may worsen sensorial (organoleptic) characteristics of drinking
water or drinks and meals prepared with such water: formation of a layer on the
surface of coffee or tea, loss of aromatic substances from meals and drinks (due
to bonding to calcium carbonate), unpleasant taste of water itself for some
consumers (calcium taste threshold is about 100 - 300
Page 15
15mg/l, unpleasant taste starts from 500 mg/l, but it also depends upon the
presence of other ions; the magnesium content exceeding 170 mg/l together with
the presence of chloride and sulphate anions are responsible for the bitter
taste of water). According to some data, increasing water hardness needs
increasing time for vegetables and meat to be cooked.Very soft water, such as
distilled and rain water as two extreme examples, is of unacceptable taste for
most people who usually report it to be of unpleasant to soapy taste. A certain
minimum content of minerals, the most crucial of which are calcium and magnesium
salts, is essential for the pleasant and refreshing taste of drinking water. At
least for this reason, demineralized drinking water should be fortified with
minerals if obtained by desalination from sea water on a ship or by
ultrafiltration from waste water on a spaceship.Optimum drinking water hardness
(Ca and Mg levels) from the health point of view For the health reasons given
above, we prefer harder water but it is not absolutely true the harder the
water, the better. An optimum is hard to set; perhaps, the following ranges
could be given: • for magnesium, a minimum of 10 mg/l (Novikov et al, 1983;
Rubenowitz et al, 2000) and an optimum of about 20-30 mg/l (Durlach et al, 1989;
Kozisek, 1992), • for calcium a minimum of 20 mg/l (Novikov et al, 1983), an
optimum about 50 (40-80) mg/l (Rachmanin et al, 1990; Kozisek, 1992), • for a
total water hardness of 2 to 4 mmol/l (Plitman et al, 1989; Lutai, 1992; Golubev
et al, 1994) – drinking water in this range was associated with the lowest rates
of different diseases as documented by the already quoted Russian
epidemiological studies.Regulatory requirements for drinking water calcium and
magnesiumThe World Health Organization in the Guidelines for drinking water
quality (WHO, 1993) evaluated calcium and magnesium from the point of view of
water hardness but did not set any either minimum or maximum recommended limits.
A reasonable requirement for the minimum required concentration of hardness
(calcium or equivalent cations) for softened and desalinated water, set up in
Council Directive 80/778/EEC (EC, 1980) appeared obligatorily in national
legislation of all EEC members. Nevertheless, this Directive remains in force to
December 2003, since Directive 98/83/EC newly entered in force since 1998 (EU,
1998). The latter directive does not present any requirement for the Ca and Mg
levels or water hardness (apart from the lower limit for pH ≥ 6.5 which requires
indirectly a certain level of dissolved solids); on the other hand, it does not
prevent the member states from implementing such a requirement, if needed, into
their national legislation. What is the position of the central European
countries in this regard? None of the EU member states (Austria, Germany) has
this indicator included in their provisions. In contrast, all of the four
candidate countries (Czech Republic, Hungary, Poland, Slovakia) have certain
requirements for the minimum Ca and Mg levels in their respective provisions,
obligatory at different degrees. The recommendations or requirements as
presented by the WHO, EU and Central European countries are reviewed in Table 1
(see Annex 1).What development is to be expected in the EU countries? If these
indicators are not reintroduced into the Directive (to be revised every 5 years
on an obligatory basis) the requirements for water Ca and Mg levels – if kept at
all – will move in most countries from the level of regulatory measures to a
lower level of unbinding regulations such as technical
Page 16
16standards (different measures for reduction of water corrosivity can be taken
as an example) or different methodical recommendations for both the water supply
sector and the public. The approach applied in the UK can be taken as an example
of health education. The Committee on Medical Aspects of Food Policy of the
Department of Health concluded: “…in view of the consistency of the
epidemiological evidence of a weak inverse associationbetween natural hardness
and cardiovascular disease mortality, it remains prudent not to undertake
softening of drinking water supplies…” (Department of Health, 1994). This
conclusion confirmed the advice that had been in place for many years and that
continue to be given by the Drinking Water Inspectorate as the drinking water
authority of the country in the leaflets for the public: „if you do install a
water softener you should make sure that you have a supply of unsoftened water
for drinking and cooking“ (Drinking Water Inspectorate, 1999).This
recommendation reflects that the cation exchange process called sodium cycle
softening is most commonly used in households today. As part of this process,
undesirable sodium is released into water while the calcium and magnesium salts
are captured. American studies showed higher incidence of hypertension, which
together with consequent lower magnesium intake are important risk factors for
CVD, among the population, including children, using sodium cycle softening for
drinking water treatment (20 to 40 % of households in the USA did so in the late
1980’s) (Das, 1988).DiscussionMost of the existing studies show that higher
water hardness (i.e. drinking water calcium and magnesium) is related to
decreased risks for CVD and especially for sudden death from CVD. This
relationship has been independently described in epidemiological studies with
different study designs, performed in different areas (with different
populations), and at different times. Consistent epidemiological observations
are supported by the data coming from autopsy, clinical, and animal studies. The
biological plausibility is high, but the specificity is less evident due to the
multifactorial aetiology of CVD. The values of the relative risks were rather
moderate or weak, but mostly statistically significant. It can be summarized
that the relationship between the calcium and magnesium intake with drinking
water and CVD stands up to most of the criteria for causality.In spite of that,
some recent papers either prudently adopt an ambiguous attitude („to date...
causality is still not proven, but there are many potential arguments in
favour...“ (Sauvant et al, 2002)) or condition possible preventive actions by
the need for further investigation or intervention studies. Intervention studies
with drinking water, which for statistical reasons would have to include very
large numbers of subjects, are not easily feasible. But are not there relevant
studies carried out in the areas where the water source has changed and where
the change in water hardness was associated with a change in mortality from CVD
as reported by the already quoted British study (Crawford et al, 1971) or a more
recent Italian study focused on comparison of mortality from CVD between two
areas supplied with water with different magnesium levels. The area supplied
with water with a low magnesium level (0.7 mg/l) showed a markedly higher CVD
mortality as compared to the area supplied with water richer in magnesium (27
mg/l). Nevertheless, later when the water source changed in the latter area and
the water Mg level decreased to less than 1 mg/l the CVD mortality increased and
became close to that of the former area (Menotti et al, 1979). Relevant is also
a large Indian food intervention study (Singh, 1990) that divided a group of 400
individuals with CVD risk into two subgroups: one strived to consume diet rich
in magnesium and the other (controls) ate normal diet. Within 10 years the
intervention group
Page 17
17showed a statistically significantly lower rates of myocardial infarction,
sudden cardiac death and total complications in the cardiovascular system. The
effect observed may not have been specific of magnesium, other diet components
may also have played a role. Successful interventions (with drinking water or
diet supplementation) were also carried out in experiments on animals (Durlach
et al, 1985; Sherer et al, 1999).Apart from the relationship between the
drinking water Ca and Mg levels and risk for CVD which is best studied and is
the most relevant from the public health point of view, it is possible that
other beneficial effects of high water Ca and Mg against some other diseases
(e.g. neurological) may manifest themselves, as documented by the above quoted
recent studies. This all offers promising prospects for preventive
measures.Several studies dealing with the relationship between magnesium
deficiency and CVD incidence also raised the question of whether Mg
supplementation could be used for the primary prevention of these diseases and
their sequelae. Several methods of supplementation have been proposed,
including: fortification of food, public education to change dietary habits,
oral supplementation, and addition of Mg to community water supplies (Eisenberg,
1992; Durlach et al, 1985; Durlach, 1989; Rylander, 1996; Bar-Dayan et al,
1997). Several questions related to possible supplementation were posed by
Eisenberg: (1) Will Mg supplementation reduce the risk of sudden death? (2) How
much time is required before the effects of such supplementation are evident?
(3) What is the optimal method of supplementation? (4) Is supplementation
technically and financially feasible? (Eisenberg, 1992).In agreement with the
focus of this article and the commonly known fact that the preventive measures
which do not require behavioural changes have always been the most effective in
public health attention will be paid to the ways of drinking water
supplementation. And we have to be serious about this question. In the light of
the high incidence and seriousness of CVD which are the leading cause of
mortality in most industrialized countries, potential effective measures even if

reducing mortality from myocardial infarction or other CVD by a small percentage


only (not to speak of the hypothetical 30% reported by some studies) could save
thousands of human lives (Rylander, 1996; Marx et al, 1997). Such an incredible
number would mean incomparable higher efficiency among any of the measures on
chemical quality of drinking water (lowering any of toxic substances below the
limit values) applied up to know.If anybody drinks low magnesium or low calcium
water, it means that he/she is at higher risk for some diseases but it does not
mean that he/she will certainly develop the disease. This situation is easily
comparable with drinking water containing a contaminant in amounts let’s say by
300% higher than the limit allowed – a man drinking such water may not develop
the disease possibly caused by the given contaminant, since the limits are
established to cover a sufficient safety factor. Nevertheless, the man is at
higher risk for the pollutant-related disease. Although the risks are
comparable, if the risk from low magnesium water is not higher, the regulatory
and enforcement mechanisms for undesirable contaminants are very strong, while
those for naturally present beneficial elements such as Mg and Ca are very weak,
if any at all.Let’s say that never in the past so much background data and
knowledge were available at time of establishing a limit for chemicals in
drinking water as they are now for magnesium
Page 18
18and calcium. Even if such an intervention measure as drinking water
fluoridation, continued in some countries to date, is taken into account.
Conclusions and recommendationsCalcium and magnesium are important parts of
drinking water and are of both direct and indirect health significance. A
certain minimum amount of these elements in drinking water is desirable since
their deficiency poses at least comparable health risk as exceedance of the
limit for some toxic substances does.Based on the available data, the desirable
minimum of magnesium and calcium can be estimated to be > 10 mg/l and > 20-30
mg/l, respectively. Nevertheless, this does not mean that if low levels of these
elements were increased to remain below the minimum mentioned above (e.g. if the
magnesium level were increased from 2 to 5 mg/l), it would be of no importance.
It seems that any increase, even by several mg/l, could have a health effect.
Although a certain minimum quantity of these elements is desirable, it
definitely does not mean the more the better. While considering higher levels of
magnesium and calcium in drinking water, not only the absolute content of these
elements but also the fact that higher water Mg and Ca levels are mostly
associated with higher levels of the other dissolved solids that may not be
beneficial to health should be taken into account.What can be called the optimum
Ca and Mg levels in drinking water ranges from 20 to 30 mg/l and from 40 to 80
mg/l, respectively, and for water hardness as Σ Ca+Mg from about 2 to 4
mmol/l.How to ensure the minimum and optimum calcium and magnesium levels in
drinking water?1) To select an adequate water source. If several water sources
are available or can be mixed, preference should be given to the sources (as a
rule, to the underground sources) containing the optimum, or at least the
minimum, Mg and Ca levels, as considered in the context of general water
composition. These sources should be in priority exploited for the drinking
(nutritional) purpose than for other, technical purposes.2) To set strict rules
for water treatment technology decreasing the amount of Ca or Mg in drinking
water (distillation, membrane technologies such as RO, ion exchange,
precipitation, etc.) or to keep some minimum content of Mg and Ca in case of
water softening or desalination. To soften drinking water only if needed for
health reasons, i.e. not for technical reasons. In the light of rapid growth in
membrane technologies and their applicability to drinking water treatment, such
rules will be more and more urgently needed.3) To promote stabilization of soft
water sources. This procedure is often used to reduce water corrosivity either
by passing the water through calcium carbonate filter (sometimes preceded by
dosing with carbon dioxide) or by adding a calcium compound such as lime milk
directly to water. Unfortunately, this results only in a negligible increase in
the magnesium level. Nevertheless, this procedure can be at least partly
optimised, on the one hand, by means of improvement of the treatment design, and
on the other hand, by selection of an adequate filtration material with a higher
magnesium content, e.g. material on a basis of CaCO3+ MgCO3or CaCO3+ MgO.
Page 19
194) To address the issue of increasing the magnesium level by addition of
magnesium salts directly to water while treated which has not been much tested
in practice. ome authors expressed their fears that it could do more harm than
good since it might disturb seriously the balance between elements or the
balance due to super saturation of CaCO3and increase corrosivity (Durlach et al,
1985). Although the first objection can be justified to some extent (the Mg to
Ca ratio of about 1:2 should be observed), the other one is not justified from
the point of view of water supply, if the resulting Mg level reaches about 10-20
mg/l.A recent case from the Czech Republic (Kyncl, 2002) has shown that central
fortification with magnesium is technically feasible: A North-Moravian water
supply company was made an offer to supply drinking water to a large Polish city
of about 100 000 population situated near the Czech-Polish border. The Polish
customer wanted the water supplied to meet the Polish decree requirement for the
indicator water hardness (60 – 500 mg/l; hardness expressed as CaCO3). Initial
hardness of the water originating from a surface source was 50 mg/l and had to
be increased to reach the minimum level required. For time and financial
reasons, the classical technology of dosing with carbon dioxide followed by
dosing with lime was not applicable and therefore addition of some soluble
magnesium or calcium salt directly to water appeared to be the only way to meet
the requirement. Four salts (magnesium chloride, calcium chloride, magnesium
sulphate, calcium sulphate) were tested in laboratory for chemical purity,
solubility and effect on pH and sensorial characteristics of water. All of the
salts tested showed acceptable results for all parameters studied up to the dose
of 20 mg/l. Finally, technical grade crystalline magnesium chloride MgCl2.6H2O
was selected because of its good solubility and lower cost. The magnesium
content was increased by about 50%, i.e. from the mean level of 3 mg/l to 4,5
(4,2-4,8) mg/l, which was sufficient to meet the minimum water hardness required
of 60 mg (equivalent CaCO3)/l. The water was supplemented at the main supply
line to the Polish city (at a flow of about 100 l/sec) for almost one year
(2001-2002). The supplementation was stopped, but not for technical reasons: the
Polish health authorities changed their position and did not require the limit
to be met any more. Mg supplementation increased the cost of water production by
about 5%. Reaching a magnesium level of 10 mg/l would increase the cost of water
production by about 20 %.Although artificial fortification of drinking water
with calcium and magnesium to a certain level is technically feasible, before
its possible regulation it would be reasonable to address the following
questions: (a) Cost/benefit assessment; (b) Is fortification of drinking water
an effective way if only about 1% of tap water is used for drinking and cooking,
and bottled water consumption is continuously increasing? (c) Is this form of
water Ca and Mg equally bioavailable as the same elements of natural origin? (We
do not know, but magnesium chloride is the most common form of therapeutical
oral Mg supplementation.) (d) Environmental impact on aquasystems (Probably no
impact); (e) To fortify to the minimum or optimum level (and what are the
minimum and optimum levels)? ince the solution of these questions may seem too
complicated, it should be noted that artificial fluoridation of community water
supply had been applied in many countries all over the world without addressing
these issues, which were of the same relevance in the case of fluorides.
Page 20
205) Public health education seems to be a quite easily applicable measure for
the moment. The public, in particular that living in the areas supplied with
water low in Ca and Mg, should be discouraged from using water softeners or
other home water treatment units removing Ca or Mg from water intended for
drinking and cooking. At the same time, the consumption of Ca/Mg-rich water
(e.g. bottled natural mineral water) could be encouraged to replace at least
partly tap (well) water low in the minerals. However, this solution is not
easily applicable to water for cooking.Introduction of regulatory measures
concerning the minimum levels of Ca and Mg in drinking water seems to be
justified and highly desirable. They should be based on the fact that it is much
simpler and much more effective to keep the existing Ca and Mg drinking water
levels than to add these minerals to water artificially. Practically, this means
restricting the use of technologies leading to removal of Ca and Mg from water
only to the cases where the Mg and Ca levels are too high (i.e. of hundreds of
mg/l or more) provided that the required minimum of Σ Ca+Mg is kept in the water
after treatment. Nevertheless, apart from this „negative“ regulation, a positive
approach should be adopted. And if Directive 98/83/EC contains some general
instructions concerning e.g. the disinfection by-products: „where possible,
without compromising disinfection, Member tates should strive for a lower
value”, why could not it give a general instruction that drinking water should
contain certain minimum Mg and Ca levels and that the member states should
strive to reach these levels?Anyway, further studies are needed to address not
only the traditional issues such as the Mg and Ca levels but also water
treatment technologies (e.g. magnetic treatment or phosphate dosing) which do
not modify the absolute levels of these elements in water but may mask the
presence or may limit the effect of these elements through different mechanisms.
Page 21
21ANNEX 1Table 1: Requirements on calcium, magnesium, or hardness in drinking
waterRequirementCountry/OrganizationRegulationValidity fromParameterUnitLimit
valueNoteWHOGuidelines for DW quality (2nd ed.)1993Hardness--WHO conclusions:
Although a number of epidem. studies have shown a statistically significant
inverse relationship between the hardness of drinking water and cardiovascular
disease, the available data are inadequate to permit the conclusion that the
association is causal. No health-based guideline value for water hardness is
proposed. calciummg/l≤ 100magnesiummg/l≤ 50(GL ≤ 30)GL…guide levelECCD
80/778/EEC1980 (-2003)total hardnessmg/l Ca≥ 60Minimum required concentration
for softened and desalinated water. Calcium or equivalent cations.EUCD
98/83/EC1998---These parameters are not included. Indirect requirement is posed
through the minimum pH value of 6.5 ( very soft water is of pH <
6.5).AustriaOrd. 304/2001 (TWV)2001---No limit value is given, but hardness is
included among the parameters to be regularly controlled in drinking
water.calciummg/l≥ 30Exceptions possiblemagnesiummg/l≥ 10Exceptions
possibleCzech RepublicDecree 376/20002001Ca + Mgmmol/lGL 0.9 – 5.0 GL…guide
level
Page 22
22GermanyOrd. TrinkwV 20002003---These parameters are not included. Indirect
requirement is posed through a minimum pH value. Indirect recommendation is
given through Article 4 (1) – see below. ⊕HungaryOrd. 201/20012001hardnessmg/l
CaO50 – 350Minimum required concentration (50 mg/l CaO) is to be met in bottled
drinking water, new water sources, and softened and desalinated
water.PolandDecree 937/20002000hardnessmg/l CaCO360 – 500Hardness expressed as
CaCO3.calciummg/lGL > 30GL…guide levelGL 10 – 30 GL…guide levelmagnesiummg/l≤
125 lovakiaDecree 29/2002 2002Ca + Mgmmol/lGL 1.1 – 5.0 GL…guide level≥ 30For
softened water.calciummg/lGL 40 – 80 Guide level.≥ 10For softened
water.magnesiummg/lGL 20 – 30 Guide level.Czech RepublicDecree revision
draft2003 ?Ca + Mgmmol/lGL 2.0 – 3.5 GL…guide level⊕ TrinkwV 2000TrinkwV 2000 in
Article 4, Clause 1 („Water … has to be fit for consumption and clean. This
requirement is considered as met, if … the generally recognized technical rules
are observed…“) refers among others to DIN 2000, which is a recognized technical
rule, and general instructions given in DIN 2000, e.g. „requirements on drinking
water quality shall be based on the characteristics of safe underground water
drawn from a sufficient depth and through sufficiently effective filter layers“
(section 5.1) or „undesirable changes in water quality caused by water treatment
should be minimized in agreement with technical rules“ (section 4.6), and thus
guarantees certain minimum levels of calcium and magnesium in drinking water.
Page 23
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